Protection of vitaminous oils



Patented Apr. 26, 1938 PATENT OFFICE PROTECTION OF VITAIWINOUS OILS Ferdinand W. Nitardy, Brooklyn, N.'Y., assignor to E. R. Squibb & Sons, New York, N. Y., a corporation of New York No Drawing.

' minous oils, particularly with respect to vitamin content and palatability.

Hydroquinone has been recognized by several investigators as useful in checking the deterioration to which the vitamins of fish-liver and vegetable oils, and the oils proper, are subject on exposure to oxygen. Hitherto the role of the hydroquinone has been deemed to be a species of negative catalysis; or at any rate it has been thought that dissolving in the oils a small proportion, less than or no more than the saturation amount, of hydroquinone could be relied on as a method of securing adequate protection for an unlimited time. Experience has shown, however, that this method of treatment cannot be depended on to safeguard the oils for the many months that often pass between the packaging of the oils and their consumption; on the contrary, oils to which an addition of this kind has been made suflfer a considerable vitamin loss, as well as a degradation of taste and odor, during the course of storage, especially if the oils encounter conditions particularly favorable to oxidation and/or if they are contained in vessels pervious to air, like gelatin capsules.

An object of this invention is the provision of a method whereby vitaminous oils may be afforded protection to a higher degree and/or for a longer period than has been possible by methods hitherto employed. A further object is the provision of vitaminous oils endowed with such protection.

It has been found that the hydroquinone functions more or less quantitatively, that it becomes progressively inactivated with lapse of time, that its preservative eflect increases with its concentration, and that vitaminous oils dissolve it too scantily-thus, a saturated solution of hydroquinone in halibut-liver oil at room temperature has a concentration of only about 0.03 percent,-

-to be protected thereby sufliciently to meet the not uncommon commercial exigencies. It was accordingly necessary to incorporate extra hydroquinone (by which is meant herein hydroquinone in excess of the concentration the vitaminous oil alonewould dissolve at room temperature) into the oil; and since solids would be less active than dissolved substances and since the presence of solids, as depositsvor sediment, would be objectionable in oils intended for internal use, it was also necessary to incorporate the extra hydro- V quinone into the oil as a solute.

In the practice of this invention the incorporation of extra hydroquinone into vitaminous oils Application August 15, 1934, Serial N0. 739,929

as a solute is made possible, and the protection of the oils is correspondingly enhanced, by adding to the oils a carrier which is miscible with the oils and in which the hydroquinone is more soluble than in the oils.

Among the suitable carriers are those in the I class embracing alcohols,'aldehydes, ethers, esters, essential oils, and essential-oil fractions. Specific examples include ethyl alcohol (absolute), normal-propyl alcohol, isobutyl alcohol, benzyl alcohol, isovaleraldehyde, salicylaldehyde, cinnamaldehyde, dimethyl ether, diethyl ether, ethyl acetate, ethyl butyrate, methyl salicylate, spearmint oil, peppermint oil, menthol. Oxidizing materials should of course not be present in the carriers, as peroxides in diethyl ether. Some carriers, on account of giving an unpleasant taste, may be unsuitable for use in oil to be drunk but satisfactory for capsuled oil. On the other hand, essential oils, besides acting as carriers, are preferred for the agreeable flavor they impart.

Among the oils to which the invention is advantageously applicable are halibut-liver oil, codliver oil, swordfish oil, various other fish and flsh-' liver oils, and vegetable oils.

By means of such carriers, vitaminous oils are enabled to hold extra hydroquinone in solution and in consequence to withstand for longer periods and/orunder more adverse conditions the deteriorative effects of oxygen on the vitamins and on the oils proper. Thus, the physical, chemical, and therapeutic stability of halibutllver oil is raised to a point where it gives full assurance for ordinary circumstances, by increasing its hydroquinone content in this manner to about 0.1 percent.

Introduction of the hydroquinone may be efiected by mere admixture of the oil with a solution of the hydroquinone in the carrier. Thus, 0.05 to 0.2 g. hydroquinone may be dissolved, with gentle warming if necessary, in 0.5 to 3.0 cc. of the carrier selected, and the solution may be well mixed with enough of the oil to make a total volume of 100 cc.

Addition to 100 cc. halibut-liver oil of 2 cc. absolute alcohol containing in solution 0.1 g.

' hydroquinone or 5 cc. absolute alcohol containing in solution 0.3 g. hydroquinone, yields, respectively, a 0.1 percent or a 0.3 percent solution of hydroquinone in halibut-liver oil. a

Mixture of 80 cc. halibut-liver oil with v5 cc. peroxide-free diethyl ether in which 0.4 g. hydroquinone has been dissolved, gives a concentration or 0.5 percent, which may be reduced to any desired degree by addition of more oil.

A 0.05 percent solution my be produced by dissolving 0.05 g. hydroquinone in 0.5 cc. nor- .mal-propyi alcohol, isobutyl alcohol, or ethyl acetate, warming ii and adding the solution to 100 cc. halibut-liver oil.

Dissolving 0.005 hydmquinone in 0.05 g. cinnamnldehyde, ethyl butyrate, peppermint oil, or menthol, and adding the solution to 10 cc. halibut-liver oil, secures a 0.05 percent concentrationoi'thehyrlroquinoneintheoil; and doubling the weight: 01 the hydroquinone and the carriers raises the on to 0.1 percent.

By slightly warming 0.05 g. hydroquinone with 0.68cc.olinndaddingthesolutionto 100cc.hniibnt-liverolithexeisobte.ineda0.05

not. Byemployingllflgorhlghydroquinone insteodofo.05g.,nndincrensingtheamountof aieumintoliiinecelsu-y,iybigher concentrations oi may be accured.

Itistobennderltoodthntthei'exnmplesnremereiyilhutntivenndbynomeens limitnflveotthe imcnflon,whichrnsybevanously'ctherwlsewithr spectto mthereintolsnloiutewiththe aidofspeumintdl.

3.1hemethcdoienhnndngtheprotection ot dlstintcomnrlses-extratherclntonsnsolutewith the nldoinnether.

immethodoi'enhnndngtheprotection of Iitnminonsoilsthat comprises incorporating exiz'athereintoasnsolute with the nidoinnalcohoi.

quinone and'en alcoholrtheietter being 1: carrier for the former.

9. Halibut-liver oil containing extra. hydroquinone and a carrier which is miscible with the halibut-liver oil and in which the hnimquinone is more soluble than in the halibut-liver oil.

10. Halibut-liver oil containing extra hydroquinoneandspearmintoiLtheletterbdnge carrier for the former.

11. The method of enhancing the protection of vitaminous oils that comprises incorporating extra. hydroqulnone therelnto as a solute with the aid oi. an essential oil.

12. Vitaminous oils containing extrn hydroquinone and an essential oil, the latter being a carrier for the former.

13. Vitaminous oils containing extra hydroquinone and diethyl ether, the latter being a 4 carrier for the former. 1

14. Vitaminous oils containing extra, hydroquinone and ethyl alcohol, the letter being n carrier for the former. A

15. mint-liver oil conteiningextrn, imiroquinone andan essential oil, the latter being a,

carrier for the former.

16. Halibut-liver oil conteinim extra hydroquinone and an ether, the latter being a carrier for the former.

17. Halibut-liver oil containing extra, hydroquinone and an alcohol, the latter being a cerrier for the former.

18. Haiilmt-iiver oil-containing extra hydroquinone nnddiethylether,thelatterbeingncar-' ri'er for the former.

19. Halibut-liver oil containing extra hydroquinone and ethyl alcohol, the latter being-n cerrier for the former.

FERDINAND W. NITARDY. 

